Durable coating compositions containing novel aspartic amine compounds

ABSTRACT

A coating composition comprising a binder of
         a. polyisocyanate crosslinking agent;   b. an isocyanate-reactive component having at least one compound having the following formula:       

                         
wherein
     X, R 1 , R 2 , p, m and n are described in the specification, or isomer or mixture of isomers thereof, two component compositions, articles coated with the novel composition and novel hydroxy amines are also part of the invention.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application Ser.No. 60/636,417, filed on Dec. 15, 2004 which are hereby incorporated byreferences in its entirely.

FIELD OF THE INVENTION

This invention is directed to coating compositions, in particular, tocoating compositions that are useful as exterior clear finishes forautomobiles and trucks.

DESCRIPTION OF THE PRIOR ART

The finishing system of choice presently being used on the exterior ofautomobiles and trucks comprises a clear coating applied over pigmentedbase coating that is applied over a primer coating. The clear coatingprovides protection, in particular, protection from weathering, to thepigmented base coating and improves the appearance of the overallfinish, in particular, provides improved gloss and distinctness ofimage. The primer coating provides adhesion to the substrate and, inparticular, provides resistance to stone chipping. When used inrefinishing of automobile and truck bodies, the clear coating isrequired to have an acceptable “pot life” and reasonably short cure timeperiod to allow for further processing or handling of the vehiclewithout damaging the finish. The term “pot life” means the period oftime after a coating is mixed with a catalyst or a crosslinking agent inwhich the composition remains at a sprayable viscosity.

The following U.S. Patents: U.S. Pat. No. 5,516,873, U.S. Pat. No.5,126,170, U.S. Pat. No. 5,243,012, U.S. Pat. No. 5,236,741, U.S. Pat.No. 5,412,056, U.S. Pat. No. 5,580,945, and U.S. Pat. No. 6,005,062,show a variety of coating composition that contain polyaspartic acidderivatives but these compositions do not have a property balance ofacceptable pot life and rapid curing time to form a sufficiently hardfinish to allow additional handling and processing of a coated vehicleor work piece after the coating composition has been applied.

To improve the rate curing, EP 0939091 uses novel amine compounds, forexample, the reaction product of 4,4′-methylene-biscyclohexanamine withtwo moles of diethyl maleate. However, coating composition formulatedwith these reactive amines do not have the desired balance of acceptablepot-life and the desired cure rate after application to an object whilemaintaining or improving on the desired properties of the resultingfinish. In an effort to improve pot life, solvents and catalysts havebeen used but solvents have a deleterious effect on VOC (volatileorganic content) emissions, which is undesirable and catalyst can resultin deterioration of film properties, such as durability. It is,therefore, desired to find a class of amine functional compounds for thereaction with isocyanates, which form coating compositions that overcomethese problems and form acceptable finishes for automotive and trucksubstrates.

EP 0743333 describes the use of simple hydroxy aspartates in thepreparation of hydroxy-functional polyhydantion prepolymers and theiruse as co-reactants for blocked polyisocyanates or aminoplast resins.The use of hydroxy-aspartates as the nucleophilic component in coatingsystems with polyisocyanates is not described. In U.S. Pat. No.5,561,214, the use of hyperbranched polyaspartate ester polymers isdescribed based on the selfcondensation of hydroxy-aspartates and thesepolymers are used as binder resins in coating systems.

The novel composition of this invention utilizes novel reactive aminecompound having less reactive hydroxy functional groups as anucleophilic component with a polyisocyanate crosslinking agent thatform coating compositions having an optimum balance of pot life andcuring time and form finishes, in particular, clear and primer finishesuseful for automobiles and trucks. The clear coatings have excellentproperties, such as, hardness, gloss, durability, weatherability, and inparticular resistance to UV (ultraviolet light) degradation,particularly when reinforced with ultraviolet light absorbers andscreeners and hindered amine light stabilizers. The primer coatingsexhibit excellent adhesion to metal substrates, in particular, aluminumand steel substrates, and provide for excellent stone chip resistance.

These compounds may be used as part of the binder component or as thesole nucleophilic component in a two component coating mixture. Whenused as the sole nucleophile, especially environmentally friendlycoating compositions may be formulated with low or even zero VOC(volatile organic content). The advancement achieved with the novelcoating compositions of this invention over the prior art is based oneffectively balancing the pot life of the coating mixture with the curecharacteristics using the unique structural characteristics of newaspartic-hydroxyl compositions in combination with polyisocyanates. Itis surprising that the use of a nucleophilic component based oncompounds of this invention which contain both aspartate and hydroxylfunctional groups in a curing reaction with polyisocyanates leads to ahigh productivity coating system with good general coating propertieswhile meeting desired environmental goals of eliminating or reducing VOCof a coating composition while maintaining a good pot life.

SUMMARY OF THE INVENTION

A coating composition comprising a binder of

-   -   a. polyisocyanate crosslinking agent;    -   b. an isocyanate-reactive component having at least one compound        having the following formula:

wherein

-   X can be independently O or N; if X equals O, n equals 1 and if X    equals N, n equals 2;    wherein-   R¹ is independently selected from H, a C₁ to C₂₀ linear or branched    alkyl group, a C₅ to C₁₆ cycloaliphatic group, a phenyl group, a C₆    to C₂₀ aryl group substituted with a C₁ to C₁₂ alkyl group,    preferred groups for R¹ are ethyl, propyl, n-butyl, sec-butyl,    cyclohexyl;    wherein-   m, on average, equals 1, 2 or 3, preferably, m, on average, equals    1;    wherein-   R² comprises the hydrocarbon radical obtained by removing the amino    and hydroxyl groups from an amino alcohol,    wherein-   p, on average, equals 1, 2 or 3.

Two component composition formulated with the above constituents andsubstrates, such as, automotive and truck bodies and parts coated withthe novel composition containing the hydroxy amine compounds are alsopart of this invention.

DETAILED DESCRIPTION OF THE INVENTION

The features and advantages of the present invention will be morereadily understood, by those of ordinary skill in the art, from readingthe following detailed description. It is to be appreciated thosecertain features of the invention, which are, for clarity, describedabove and below in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures of the invention that are, for brevity, described in thecontext of a single embodiment, may also be provided separately or inany sub-combination. In addition, references in the singular may alsoinclude the plural (for example, “a” and “an” may refer to one, or oneor more) unless the context specifically states otherwise.

The use of numerical values in the various ranges specified in thisapplication, unless expressly indicated otherwise, are stated asapproximations as though the minimum and maximum values within thestated ranges were both preceded by the word “about.” In this manner,slight variations above and below the stated ranges can be used toachieve substantially the same results as values within the ranges.Also, the disclosure of these ranges is intended as a continuous rangeincluding every value between the minimum and maximum values.

All patents, patent applications and publications referred to herein areincorporated by reference in their entirety.

A typical auto or truck body is produced from a steel sheet or a plasticor a composite substrate. For example, the fenders may be of plastic ora composite and the main portion of the body of steel. If steel is used,it is first treated with an inorganic rust-proofing compound, such as,zinc or iron phosphate and then a primer coating is applied generally byelectrodeposition. Typically, these electrodeposition primers areepoxy-modified resins crosslinked with a polyisocyanate and are appliedby a cathodic electrodeposition process. Optionally, a primer can beapplied over the electrodeposited primer, usually by spraying, toprovide better appearance of a base coating or a mono coating appliedover the primer and to improve the adhesion of such coatings to theprimer or both of the above. A mono coating of a pigmented coatingcomposition then can be applied but preferably, a pigmented base coatingwith a clear top coating is applied to form a clear coat/color coatfinish on the truck or automobile body or auto or truck part. Usually,after application, each of the coatings is cured by baking at anelevated temperature. It is generally known that a clear top coating canbe applied over the base coating and both coatings cured together at anelevated temperature.

When refinishing automobile and truck bodies, the original OEM topcoatis usually sanded and a primer or sealer coat applied and then a monocoat or a basecoat/clear coat is applied. These coatings are usuallycured at ambient temperatures or at slightly elevated temperatures, suchas, 40 to 100° C.

A “clear coating composition” for automotive use is a composition thatforms a transparent finish upon curing and typically has a DOI(distinctness of image) of more than 70 and a 20° gloss of more than 70.These clear coatings provide a glossy in depth appearance to the finishon the automobile or truck and therefore, are required to have goodgloss and distinctness of image. Also, the clear finish also provides aprotective finish that is durable and resistant to scratching, marringand chipping and also provides resistance to weathering, in particularto U.V. degradation and photo-oxidation.

A “matte clear coating composition” can also be used, for example forthe interior of an automobile or truck. These matte finishes have asubstantially lower gloss, for example, a 20° gloss of 20 or less andvery low DOI.

Typical “primer compositions” provide adhesion to a substrate and forthe novel compositions of this invention provide excellent adhesion tobare metal substrates, such as, steel and aluminum, and to treated metalsubstrates, such as galvanized steel, and provide a surface to which thetopcoat, such as, a pigmented mono coat or the basecoat of a base coatclear coat finish.

The term “binder” as used herein refers to the film forming constituentsof the composition that include the isocyanate reactive component, i.e.,having functional groups that are reactive with isocyanates andcomprising active hydrogen, and optional polymeric and/or oligomericcomponents, polyisocyanate crosslinking agents and optional reactivediluents, such as, ketimines and aldimines and optional acrylicnon-aqueous dispersions. Solvents, pigments, catalysts, rheologymodifiers, antioxidants, U.V. absorbers, hindered amine lightstabilizers, antioxidants, in particular disubstituted phenoliccompounds, hydroperoxide decomposers, leveling agents, antifoamingagents, anti-cratering agents, adhesion promoting agents are notincluded in the term.

Molecular weight (both number and weight average) is determined by gelpermeation chromatography utilizing a high performance liquidchromatograph supplied by Hewlett-Packard, Palo Alto, Calif. and unlessotherwise stated the liquid phase used was tetrahydrofuran and thestandard was polymethylmethacrylate or polystyrene.

“Tg” (glass transition temperature) is in ° C. and determined byDifferential Scanning Calorimetry or calculated according to the FoxEquation.

Typically, the binder of the novel composition comprises 20 to 80% byweight, based on the weight of the binder, of the isocyanate reactivecomponent or hydroxyl containing aspartic acid derivative and 20 to 80%by weight, based on the weight of the binder, of a polyisocyanatecrosslinking agent. The stochiometric ratio of isocyanate functionalityto isocyanate reactive component is 0.5 to 3.0, preferably, 0.8 to 2.0and most preferably, 1.0 to 1.5. Optionally, the binder can contain upto 75% by weight, preferably, 5 to 60% by weight, and most preferably, 5to 30% by weight, based on the weight of the binder, of a polymeric oroligomeric component or both wherein the component contains groups thatare reactive with the polyisocyanate crosslinking agent. One preferredbinder composition contains 25 to 50%, by weight of the isocyanatereactive component, 5 to 30% by weight of the polymeric or oligomericcomponent or both and 20 to 70% by weight of a polyisocyanate, whereinthe sum of all of the components of the binder is 100%. Anotherpreferred binder composition contains the isocyanate reactive componentor hydroxyl containing aspartic acid derivative as the sole nucleophiliccomponent that is reactive with the polyisocyanate.

Particular advantages of the novel coating composition of this inventionis that it provides a protective clear finish that has an excellentbalance between pot life and cure characteristics once applied to theobject. Also, the resulting finish has good gloss and distinctness ofimage that provides an excellent appearance. The finish hardens in areasonably short time after application and has excellentweatherability, in particular, resistance to U.V. degradation andphoto-oxidation when properly reinforced with the appropriate additives.When the novel composition is used to refinish automobiles and trucks,it has excellent adhesion to metal substrates and cures to a tack freestate in a relatively short period of time under ambient temperatures orunder slightly elevated drying temperatures, for example, 40 to 100° C.,that allows a coated vehicle to be moved or further processed withoutdamage to the finish.

The novel composition of this invention can contain pigments and isuseful as a pigmented mono-coat topcoat, as a pigmented base coat of abase coat/clear coat finish or as a primer or primer surfacer, whichcures in a relatively short period of time to allow for subsequentapplication of topcoats, basecoat/clear coats or monocoats. The novelcomposition can also be used for OEM (original equipment manufacture) ofautomobiles, trucks and parts thereof.

The novel composition may be solvent based and has a solids content offilm forming binder of 20 to 90% by weight, preferably, 40 to 80% byweight. It may be possible to formulate a 100% solids composition usingthe compounds of this invention. In addition, reactive diluents can beused to formulate high solids compositions and applied at highviscosities, e.g., using airless spray equipment or can be used as aputty.

An aqueous liquid carrier, which typically is water but may containother liquids, may be used in place of the solvent. Before application,a sufficient amount of liquid usually is added, for example, water orsolvents, to reduce the composition to a spray viscosity. In the eventthat the novel coating composition is an aqueous composition, the pH ofthe composition typically is 6.0 to 10.0 and preferably, 7.5 to 8.5.

The isocyanate reactive component of the novel composition is anaspartic acid derivative and has the formula (I)

wherein

-   X can be independently O or N; if X equals O, n equals 1 and if X    equals N, n equals 2;    wherein-   R¹ is independently selected from H, a C₁ to C₂₀ linear or branched    alkyl group, a C₅ to C₁₆ cycloaliphatic group, a phenyl group, a C₆    to C₂₀ aryl group substituted with a C₁ to C₁₂ alkyl group,    preferred groups for R¹ are ethyl, propyl, n-butyl, sec-butyl,    cyclohexyl;    wherein-   m, on average, equals 1, 2 or 3, preferably, m, on average, equals    1;    wherein-   R² comprises the hydrocarbon radical obtained by removing the amino    and hydroxyl groups from an amino alcohol,    wherein-   p, on average, equals 1, 2 or 3.

The aspartic acid derivatives suitable for the coating compositions ofthis invention may be prepared by reacting optionally substituted maleicor fumaric acid derivatives with amino alcohols.

The isocyanate reactive compounds of this invention are prepared in areaction of the amino alcohol substrate with a maleic or fumaric acidderivative of the general formula (II)

with R¹ and X as described above.

For the synthesis of the isocyanate reactive components of thisinvention useful maleic or fumaric acid derivatives are for exampledimethyl maleate, diethyl maleate, di-n-butyl maleate, di-sec-butylmaleate, dicyclohexyl maleate, tetraethylmaleamide,tetrapropylmaleamide, (Z)-1,4-di(piperidin-1-yl)but-2-ene-1,4-dione,diethylmaleamide, (Z)-methyl 3-(butylcarbamoyl)acrylate, (Z)-ethyl3-(dipropylcarbamoyl)acrylate and the corresponding fumaric acidderivatives. The preparation of the isocyanate reactive components ofthis invention from the indicated starting materials may be carried outin a temperature range of 0 to 100° C. The mole-ratios of startingmaterials used of these reactions are such that for each primary aminefunctional group at least one and preferentially one equivalent ofmaleic or fumaric acid derivative is used. Optionally, startingmaterials which are used in excess in this reaction can be separatedfrom the product mixture using methods known to those skilled in theart, such as distillation or chromatography. The reaction can be carriedout using the starting materials directly or in the presence of asolvent such as methanol, ethanol, propanol, tetrahydrofuran, dioxan,toluene, xylenes, acetonitrile, dimethylformamide, pyridine or mixturesof such solvents.

The choice of the specific structure of the amino alcohol used on thisinvention is critical to the overall coatings properties of the coatingscompositions of this invention. The amino alcohols used in thisinvention are described in the following embodiments.

Suitable amino alcohols for the preparation of the aspartic acidderivatives of this invention as described in this first embodiment arebased on general formula (IV):

wherein

p has a value of 1 to 3, preferably 1 or 2,

and R² represents a hydrocarbyl radical obtained by removing the aminoand hydroxyl groups from the of formula (IV) amino alcohol.

Suitable amino alcohols include ethanolamine, 1-amino-2-hydroxypropane,1,3-propanolamine, (a commercial product from BASF Intermediates), theisomeric butanolamines, 1,5-pentanolamine and 1,6-hexanolamine (bothcommercial products from BASF Intermediates),2-(hydroxyethoxy)ethylamine (product by BASF Intermediates), isomericmixtures of amino-cyclooctanol (as described in DE 1077658), isomericmixtures of amino-cyclododecanol (as described as byproducts in WO03027052), 4-aminomethylcyclohexanemethanol (as described in U.S. Pat.No. 3,137,727 and in U.S. Pat. No. 3,143,570),4-aminomethylcyclohexanepropanol,(4-(aminomethyl)-3-ethylcyclohexyl)methanol,4-[(4-amino-cyclohexyl)-methyl]-cyclohexanol (as described in DE1468779), bis-(2-hydroxypropyl)aminopropylamine andbis-(2-hydroxyethyl)aminopropylamine, both products of Tomah, and2-(2-aminoethoxy)ethanol, product of BASF.

Furthermore, other suitable amino alcohols for the preparation of theaspartic acid derivatives of this invention are described in this secondembodiment with —R²—[OH]_(p) in general formula (IV) described byformula (V):

wherein

-   the exact point of attachment and orientation of the —CH₂—B— group    (which also connects to the amine nitrogen atom) and the R²⁰—R²⁶    groups to the norbornane skeleton can vary and mixtures of compounds    and isomers are commonly utilized by this invention;-   the —(CH₂)_(q)— group in Formula (V) attaches to the amine group in    Formula (IV);-   k equals 0, 1 or 2 and, when k equals 1 or 2, the additional    bridging CH₂ group(s) may be on the same or opposite side with    respect to the first bridging CH₂ group;-   B equals (—(CH₂)_(t)—(CH)—(CH₂)_(s)—)_(r), r=0 or 1, s+t=1 to 16,    with the —(CH)— group connecting to the —(CH₂)_(q)— group, in which    B forms a ring connecting to the norbornane skeleton in place of one    of R²⁰, R²¹ or R²² substituents;-   R²⁰, R²¹, and R²² can be the same or different and are each    independently H, a C₁ to C₂₀ linear or branched alkyl group;

q is equal to 1, 2, 3, or 4;

-   R²³, R²⁴, R²⁵ and R²⁶ can be the same or different and are each    independently H, a C₁ to C₂₀ linear or branched alkyl group;-   with the proviso that at least one substituent independently    selected from R²³ R²⁴, R²⁵ and R²⁶ is a —OH group, or a C₁ to C₂₀    linear or branched alkyl group bearing a hydroxyl group.

Exemplary cycloaliphatic compounds of structure (V) which correspond to—R²— [OH]_(p) of general formula (IV) include those represented byFormulae (VI)-(XIX) as shown below.

and isomers of any of the above.

According to general structure (IV), the above listed cycloaliphaticalcohol radicals in Formulae (VI)-(XIX) each connect to an NH₂ group torepresent novel cycloaliphatic amino alcohol compounds that are used inthis invention.

The norbornene derivatives used as starting materials in this embodimentof the invention contain a substituted norbornene(bicyclo[2.2.1]heptene) fragment which may be further reacted byhydrocyanation or by hydroformylation. Products of these processes are,for example, nitrile aldehyde norbornane derivatives. These substitutednorbornene starting materials can be prepared using procedures known inthe literature. Typical examples are described in Organic Chemistry,3^(rd) Edition, Peter Vollhardt and Neil Schore, New York, Freeman andCompany, 1998, pg 600, or in U.S. Pat. No. 5,861,528, U.S. Pat. No.6,100,323, or U.S. Pat. No. 5,284,929.

Certain cycloaliphatic amino alcohol compounds (for example (VIII),(IX), (XIV)-(XIX)) may be derived from the nitrile-ester precursor.These cycloaliphatic nitrile derivatives can be prepared as described inU.S. Publication No. 20050159614, published Jul. 21, 2005. Thecorresponding cycloaliphatic amine derivatives can be prepared asdescribed in U.S. Publication No. 20050159626, published Jul. 21, 2005.The entire disclosure of these applications is incorporated herein byreference. These nitrile ester compounds may be hydrogenated to thecorresponding amino alcohol compounds while the hydrogenation of thecarboxylic acid or ester functional group may be carried out followingprocedures outlined in JP54145650, JP00355564.

Certain cycloaliphatic amino alcohol compounds, for example, compound(XII), may be derived from a hydroboration—oxidation reaction asdescribed for example in Chemische Berichte (1989), 122(5), 975-84followed by a hydrogenation reaction.

Certain cycloaliphatic amino alcohol compounds, for example compound(VI), (VII), (X), (XII)-(XIV), (XVI), may be derived from ahydroformylation process in combination with a hydrogenation process.For example, compound (Vl) may be derived from5,6-cyano-bicyclo-[2.2.1]-heptane-2-carboxaldehyde which may be derivedfrom cyano-bicyclo-[2.2.1]-heptane in a hydroformylation reaction. Aprocess for this transformation has been described in U.S. Pat. No.2,956,977, EP82-104243, JP60072844, WO2001007382. Other derivatives aslisted above may be prepared using a similar process. However, it ispreferred to produce the composition of the invention by the processdisclosed below. The amino-alcohols of this invention may be formed in ahydrogenation reaction by the process disclosed below using nitrile,aldehyde or other carboxylic acid derivatives as precursors.

A process of preparing the amino-alcohol compounds of this invention(for example (VI), (VII), (X), (XII)-(XIV), (XVI)) may be carried out ina two step process of hydroformylation followed by hydrogenation.Alternatively, both reaction steps may be combined into one process stepin which the hydroformylation and the hydrogenation of the formedaldehyde functional group occur in the same reaction step. Thehydroformylation process comprises contacting the precursorcycloaliphatic nitrile derivative, with a gas mixture of CO and hydrogenin the presence of a catalyst at a temperature in the range from about50° C. to about 150° C., preferably about 80° C. to about 110° C., undera pressure that can accommodate the temperature range, preferably in therange of from about 50 to about 10,000 kPa for a period of from about 1minute to about 72 hours.

The hydroformylation process comprises reacting a monoethylenicallyunsaturated nitrile compound with a source of CO and H₂ in the presenceof a catalyst precursor composition comprising a transition metalselected from the group of Co, Rh, Ru, Ir, Pd, and Pt, and at least twomonodentate or one multidentate ligand, typical examples aretriphenylphosphite or triphenylphosphine.

The reaction conditions of the hydroformylation process according tothis invention are in general the same as used in a conventionalprocess, described, for example, in U.S. Pat. No. 4,769,498, which isincorporated herein by reference and will be dependent on the particularstarting ethylenically unsaturated organic compound. For example, thetemperature can be from room temperature to 200° C., preferably from50-120° C. The pressure may vary from atmospheric pressure to 20 MPa,preferably from 0.15 to 10 MPa and more preferably from 0.2 to 1 MPa.The pressure is, as a rule, equal to the combined hydrogen and carbonmonoxide partial pressure. Extra inert gases may however be present. Themolar ratio of hydrogen to carbon monoxide is generally between 10 to 1and 1 to 10, preferably between 6 to 1 and most preferably 1 to 2.

The amount of rhodium compound is not specially limited, but isoptionally selected so that favorable results can be obtained withrespect to catalyst activity and economy. In general, the concentrationof rhodium in the reaction medium is between 10 and 10,000 ppm and morepreferably between 50-500 ppm, calculated as the free metal.

The molar ratio of monodentate or multidentate phosphorus ligand torhodium is not specially limited, but is optionally selected so thatfavorable results can be obtained with respect to catalyst activity,aldehyde selectivity, and process economy. This ratio generally is fromabout 0.5 to 100 and preferably from 1 to 10 (moles of ligand to molesof metal).

The choice of solvent is not critical provided the solvent is notdetrimental to catalyst, reactant and product. The solvent may be amixture of reactants, such as the starting unsaturated compound, thealdehyde product and/or by-products. Suitable solvents include saturatedhydrocarbons, such as, kerosene, mineral oil or cyclohexane, ethers,such as, diphenyl ether, tetrahydrofuran or a polyglycol, ketones, suchas, methyl ethyl ketone and cyclohexanone, nitrites, such as,methylglutaronitrile, valeronitrile, and benzonitrile, aromatics, suchas, toluene, benzene and xylene, esters, such as, methyl valerate andcaprolactone, dimethyl-formamide, and sulfones, such as,tetramethylenesulfone. The reaction may also be conducted with reactantsand products in the gas phase.

Preferably, when a liquid reaction medium is used, the reaction mixtureis agitated, such as by stirring or shaking.

The hydroformylation process according to the invention can be performedas described below:

The preferred temperature range is from about 50° C. to about 180° C.,most preferably from about 90° C. to 110° C. The temperature must bechosen so as to maintain all of the reactants and products in the vaporphase, but low enough to prevent deterioration of the catalyst. Theparticular preferred temperature depends to some extent on the catalystbeing used, the olefinic compound being used, and the desired reactionrate. The operating pressure is not particularly critical and canconveniently from about 1-10 atmospheres (101.3 to 1013 kPa). Thepressure and temperature combination must be chosen so as to maintainreactants and products in the vapor phase.

The method for making certain amino alcohols of the present inventioninvolves a hydrogenation process of molecules containing aldehyde andnitrile moieties, either alone or as mixtures of isomers or mixtures ofcompounds.

The compounds or mixtures of compounds may be contacted with hydrogen inthe presence of a catalyst, optionally, in the presence of a solventand/or a promoter to yield molecules comprising alcohol and aminemoieties. The process comprises the reduction of both the aldehyde andthe nitrile moiety and may be conducted in one reaction step or in twosequential reaction steps, with isolation of molecules containingalcohol and nitrile moieties.

During the hydrogenation process the feed (i.e., molecules containingaldehyde and nitrile moieties either alone or in mixtures of isomers) iscontacted with hydrogen. The mole ratio of hydrogen to feed is notcritical as long as sufficient hydrogen is present to produce thedesired products. Hydrogen is preferably used in excess. Hydrogenpressures are generally in the range of about 340 kPa-17240 kPa (50-2500psig), with 689 to 8274 kPa (100-1000 psig) preferred. The hydrogenationprocess can be conducted at temperatures from 40° C. to about 180° C.,preferably from 55° C. to about 100° C.

Preferred catalysts for hydrogenating the feed comprise one or moreelements from the series of transition metals, particularly useful arecobalt, nickel, copper, ruthenium, rhodium, palladium and combinationsthereof. The hydrogenation catalyst may also comprise one or moreelements in addition to the transition metals mentioned above, includingbut not limited to chromium, titanium, gold, iron and platinum. Thehydrogenation catalyst can also be in the form of an alloy, including asolid solution of two or more elements. The hydrogenation catalyst canalso be a homogeneous catalyst capable of hydrogenating aldehydes andnitrites, e.g., rhodium or ruthenium complexes bearing phosphine orphosphite ligands.

The transition metal for hydrogenation can also be supported on aninorganic support, such as, alumina, magnesium oxide and combinationsthereof. The metal can be supported on an inorganic support by any meansknown to one skilled in the art such as, for example, impregnation,co-precipitation, ion exchange, or combinations of two or more thereof.

The metal can be reduced before the hydrogenation reaction by any meansknown to one skilled in the art such as, for example, pretreatment withhydrogen, formaldehyde or hydrazine.

The hydrogenation catalyst can be present in any appropriate physicalshape or form. It can be a homogeneous catalyst, a heterogenizedhomogeneous catalyst or it can be in fluidizable forms, powders,extrudates, tablets, spheres or combinations of two or more thereof. Thehydrogenation catalyst may be in sponge metal form, for example, theRaney® nickels and Raney® cobalts. The molar ratio of hydrogenationcatalyst to feed can be any ratio as long as the ratio can catalyze thehydrogenation. The weight ratio of hydrogenation catalyst to feed isgenerally in the range of from about 0.0001:1 to about 1:1, preferablyabout 0.001:1 to about 0.1:1. If the catalytic element is supported onan inorganic support or is a portion of an alloy or solid solution, thecatalytic element is generally present in the range of from about 0.1 toabout 60, preferably about 1 to about 50, and most preferably about 2 toabout 50 weight percent based on the total hydrogenation catalystweight.

The hydrogenation can optionally be conducted in the presence of asolvent. Suitable solvents include those known in the art as useful forhydrogenation reactions. Examples of these are amines, aliphaticalcohols, aromatic compounds, ethers, esters (including lactones), andamides (including lactams). Specific examples of solvents include:ammonia, toluene, tetrahydrofuran, methanol, ethanol, any isomericpropanol, any isomeric butanol and water. Preferred solvents includetetrahydrofuran, ammonia and methanol. It will be appreciated that thesolvent may serve to reduce the viscosity of the system to improvefluidity of the catalyst in the reaction vessel, as well as serve toremove the heat of reaction from the feed and products. The solvent maybe present in a range of 1% to 75% by weight of the total reactionmixture, excluding the catalyst, preferably from 10% to 50%.

Optionally, a promoter may be used in the hydrogenation process to alterthe rate of the reaction and/or to alter the selectivity of thereaction. Suitable promoters include water, mineral acids, alkali oralkaline earth metal hydroxides, quaternary ammonium hydroxides,quaternary ammonium cyanides, quaternary ammonium fluorides, andcombinations of these. Promoters may be present at from 10 ppm to 3% byweight of the total reaction mixture, excluding the catalyst, preferablyfrom 50 ppm to 1.5%.

Preferably the process is conducted in two sequential steps. In thefirst step the aldehyde moieties are hydrogenated to primary alcoholmoieties. The preferred aldehyde hydrogenation conditions comprise aruthenium supported on carbon catalyst, 50-80° C., and 689-3447 kPa(100-500 psig). The preferred nitrile hydrogenation conditions comprisea catalyst of the sponge nickel or cobalt type, 70-100° C., and3447-8274 kPa (500-1200 psig). Commercially available sponge metalcatalysts are promoted or un-promoted Raney® Ni or Raney® Co catalyststhat can be obtained from the W.R. Grace and Co. (Chattanooga, Tenn.),or alternative sponge metal catalysts available, for example, fromActivated Metals Corporation (Sevierville, Tenn.) or Degussa(Parsippany, N.J.). Commercially available ruthenium on carbon catalystsor other supported catalysts are available from Engelhard Corporation(Iselin, N.J.) or Degussa (Parsippany, N.J.).

Preferred aspartic-hydroxyl compositions of this invention are shown informulae (XX)-(XXXIII):

and isomers of any of the above.

The novel coating composition can contain optional polymeric components.These components have groups that are reactive with isocyanate and canbe used in an amount of up to 75% by weight, preferably, 1-60% byweight, based on the weight of the binder. One preferred polymericcomponent is an acrylic polymer. Typically useful acrylic polymers havea number average molecular weight of about 5,000 to 50,000, a Tg of 10to 80° C. and contain moieties, such as, hydroxyl, carboxyl, glycidyland amino groups. Typically useful acrylic polymers are those known inthe art and are polymers of two or more of the following: linearalkyl(meth)acrylates having 1 to 12 carbon atoms in the alkyl group,cyclic or branched alkyl(meth)acrylates having 3 to 12 carbon atoms inthe alkyl group including isobornyl (meth)acrylate, hydroxyalkyl(meth)acrylates having 1 to 4 carbon atoms in the alkyl group,glycidyl(meth)acrylate, hydroxy amino alkyl(meth)acrylates having 1 to 4carbon atoms in the alkyl group, and can contain styrene, alpha methylstyrene, vinyl toluene, (meth)acrylonitrile (meth)acryl amides,(meth)acrylic acid, (meaning both acrylic acid and methacrylic acid)trimethoxysilylpropyl(meth)acrylate and the like.

Preferred are hydroxy functional acrylic polymers having a hydroxyequivalent weight of 300 to 1300 and are polymers of hydroxy alkyl(meth)acrylates and one or more of the aforementioned monomers. Onepreferred hydroxy containing acrylic polymer contains 35 to 50% byweight styrene, 15 to 25% by weight ethylhexyl methacrylate and 15 to20% by weight isobornyl methacrylate and 20 to 30% by weighthydroxyethyl methacrylate. A particularly preferred acrylic polymercontains 37% styrene, 20% by weight 2-ethylhexyl methacrylate and 17.5%by weight of isobornyl methacrylate and 25.5% by weight hydroxyethylmethacrylate.

Acrylic oligomers having a number average molecular weight of 300 to3,000 of the aforementioned monomeric components also can be used as theoptional polymeric component. By using monomers and reactants well knownto those skilled in the art, these oligomers can have the one or more ofthe following groups that are reactive with isocyanate: hydroxyl,carboxyl, glycidyl, amine, aldimine, phosphoric acid and ketimine.Typically useful acrylic oligomers are disclosed in FA 1048 Ser. No.10/617,585 filed Jul. 11, 2003, Publication No. U.S. 2004-001009published on Jan. 15, 2004, which is hereby incorporated by reference.

Polyesters can also be used as the optional polymeric component, suchas, hydroxyl or carboxyl terminated or hydroxyl or carboxyl containingpolyesters. The following are typically useful polyesters or esteroligomers: polyesters or oligomers of caprolactone diol and cyclohexanedimethylol, polyesters or oligomers of tris-hydroxy ethylisocyanurateand caprolactone, polyesters or oligomers of trimethylol propane,phthalic acid or anhydride and ethylene oxide, polyesters or oligomersof pentaerythritol, hexahydrophthalic anhydride and ethylene oxide,polyesters or oligomers of pentaerythritol, hexahydrophthalic anhydrideand butylene oxide, such as those shown in U.S. Pat. No. 6,221,494 B1which is hereby incorporated by reference.

The aforementioned polyesters and oligomers can be reacted with anorganic isocyanate to form urethane polymers and oligomers that can beused as the optional polymeric component in the novel composition.

One useful urethane oligomer that can used in the novel composition isformed by reacting an aliphatic polyisocyanate with an aliphatic orcycloaliphatic monohydric alcohol and subsequently reacting theresulting composition with a hydroxy functional aliphatic carboxylicacid until all of the isocyanate groups have been reacted. One usefulpolyurethane oligomer comprises the reaction product of the isocyanurateof hexane diisocyanate, cyclohexanol and dimethylol propionic acid. Awater dispersible oligomer can be formed using conventional techniquesknown to those skilled in the art.

Optionally, an oligomeric component having a number average molecularweight of 300 to 3,000 having reactive groups that crosslink with anisocyanate, where the reactive groups are hydroxyl, carboxyl, glycidyl,amine, aldimines, phosphoric acid, ketimine and any mixtures thereof canbe added to the novel composition.

Typically useful organic polyisocyanates crosslinking agents that can beused in the novel composition of this invention include aliphaticpolyisocyanates, cycloaliphatic polyisocyanates and isocyanate adducts.Examples of suitable aliphatic and cycloaliphatic polyisocyanates thatcan be used include the following: 4,4′dicyclohexyl methanediisocyanate, (“H₁₂MDI”), trans-cyclohexane-1,4-diisocyanate,1,6-hexamethylene diisocyanate (“HDI”), isophorone diisocyanate,(“IPDI”), other aliphatic or cycloaliphatic di-, tri- ortetra-isocyanates, such as, 1,2-propylene diisocyanate, tetramethylenediisocyanate, 2,3-butylene diisocyanate, octamethylene diisocyanate,2,2,4-trimethyl hexamethylene diisocyanate, dodecamethylenediisocyanate, omega-dipropyl ether diisocyanate, 1,3-cyclopentanediisocyanate, 1,2 cyclohexane diisocyanate, 1,4 cyclohexanediisocyanate, 4-methyl-1,3-diisocyanatocyclohexane,dicyclohexylmethane-4,4′-diisocyanate, 3,3′-dimethyl-dicyclohexylmethane4,4′-diisocyanate, polyisocyanates having isocyanurate structural units,such as, the isocyanurate of hexamethylene diisocyanate and theisocyanurate of isophorone diisocyanate, the adduct of 2 molecules of adiisocyanate, such as, hexamethylene diisocyanate, uretidiones ofhexamethylene diisocyanate, uretidiones of isophorone diisocyanate and adiol, such as, ethylene glycol, the adduct of 3 molecules ofhexamethylene diisocyanate and 1 molecule of water, allophanates,trimers and biurets of hexamethylene diisocyanate, allophanates, trimersand biurets of isophorone diisocyanate and the isocyanurate of hexanediisocyanate.

Tri-functional isocyanates also can be used, such as, Desmodur® N 3300,trimer of hexamethylene diisocyanate, Desmodur® 3400, trimer ofisophorone diisocyanate, Desmodur® 4470 trimer of isophoronediisocyanate, these trimers are sold by Bayer Corporation. A trimer ofhexamethylene diisocyanate sold as Tolonate® HDT from Rhodia Corporationis also suitable.

An isocyanate functional adduct can be used, such as, an adduct of analiphatic polyisocyanate and a polyol. Also, any of the aforementionedpolyisocyanates can be used with a polyol to form an adduct. Polyols,such as, trimethylol alkanes, particularly, trimethylol propane orethane can be used to form an adduct.

The novel composition can contain 1 to 30% by weight, based on theweight of the binder of acrylic NAD (non-aqueous dispersed) resins.These NAD resins typically are high molecular weight resins having acrosslinked acrylic core with a Tg between 20 to 100° C. and attached tothe core are low Tg stabilizer segments. A description of such NADs isfound in Antonelli et al. U.S. Pat. No. 4,591,533 and in Barsotti et al.U.S. Pat. No. 5,763,528 which patents are hereby incorporated byreference.

Optionally, a catalyst may be used in the novel composition to reducecuring time and temperature and allow curing of the coating at ambienttemperatures. Useful catalysts include those known to the person skilledin the art, like, alkyl carboxylic acids having 1 to 12 carbon atoms inthe alkyl group, such as, acetic acid, formic acid, glycolic acid;aromatic acids, such as, benzoic acid; and oligomers having pendant acidgroups.

The coating composition optionally may also include a catalyticallyactive amount of one or more tin or tertiary amine catalysts foraccelerating the curing process. Generally, catalytically active amountsof the catalyst in the coating composition range from about 0.001percent to about 5 percent, preferably from 0.005 percent to 2 percent,more preferably from 0.01 percent to 1 percent, all in weight percentbased on the weight of the binder. A wide variety of catalysts can beused, such as, tin compounds, including stannous octoate, stannicchloride, butyltin trichloride, dibutyl tin dilaurate (DBTDL),dibutyltin-bis(dodecyl mercaptan), di(2-ethylhexyl)tin oxide, dibutyltin diacetate, dibutyltin sulfonamide, and dibutyltin dibutoxide (DBTO);tertiary amines, such as, triethylamine, tributylamine,N-methylmorpholine, N-ethylmorpholine, N,N.N′,N′-tetramethylethylenediamine, pentamethyldiethylene triamine, 1,4-diazabicyclo[2.2.2]octane(DABCO), N-methyl-N′-(dimethylaminoethyl)-piperazine,N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine,N,N-diethylbenzylamine, bis(N,N-diethylaminoethyl) adipate.N,N,N′,N′-tetramethyl-1,3-butanediamine,N,N-dimethyl-1,3-phenylethylamine, 1,2-dimethylimidazole,1-methylimidazole, 2-methylimidazole. Especially also the combination oftertiary amines and tin compounds may be used as catalyst. One of thecommercially available catalysts, sold under the trademark, Fastcat®4202 dibutyl tin dilaurate by Elf-Atochem North America, Inc.Philadelphia, Pa., is particularly suitable. Commercially availabletertiary amines include 1,2-dimethylimidazole and 1-methylimidazole byBASF AG, 1,4-diazabicyclo[2.2.2]octane (DABCO® crystalline) by AirProducts, and N,N.N′,N′-tetramethylethylene diamine (TOYOCAT-TE) byTOSOH. Other catalyst may also be used for this reaction such as, Al,Ti, Bi or Zr catalyst, K-Kat 348 (bismuth carboxylate), K-Kat 4205(Zirconium chelate 2,5-pentanedione), K-Kat 5218 (Aluminum chelatecomplex), K-Kat XC-6212 (Zirconium complex), acid catalysts such as paratoluene sulfonic acid or dodecyl benzene sulfonic acid, typicallyavailable from King Industries. The use of these described catalysts andespecially the combination of these catalysts allows the formulation ofthe amino-alcohol oligomers of this invention with the desired improvedpotlife along with the desired cure characteristics and the desired filmproperties.

When used as a clear coating or mono-coat composition, the novelcomposition optionally contains about 0.1 to 5% by weight, based on theweight of the binder, of ultraviolet light absorbers. Typically usefulultraviolet light absorbers include hydroxyphenyl benzotriazols, suchas, 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert.amyl-phenyl)-2H-benzotriazole,2[2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, reactionproduct of 2-(2-hydroxy-3-tert.butyl-5-methylpropionate)-2H-benzotriazole and polyethylene ether glycol having aweight average molecular weight of 300,2-(2-hydroxy-3-tert.butyl-5-iso-octyl propionate)-2H-benzotriazole;hydroxyphenyl s-triazines, such as,2-[4((2,-hydroxy-3-dodecyloxy/tridecyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4(2-hydroxy-3-(2-ethylhexyl)-oxy)-2hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine,2-(4-octyloxy-2-hydroxyphenyl)4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;hydroxybenzophenone U.V. absorbers, such as, 2,4-dihydroxybenzophenone,2-hydroxy-4-octyloxybenzophenone, and2-hydroxy-4-dodecyloxybenzophenone.

When used as a clear coating or mono-coat composition, the novelcomposition optionally contains about 0.1 to 5% by weight, based on theweight of the binder, of a di-substituted phenol antioxidant or ahydroperoxide decomposer. Typically useful antioxidants includetetrakis[methylene(3,5-di-tert-butylhydroxy hydrocinnamate)]methane,octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,tris(2,4-di-tert-butylphenyl) phosphite,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trioneand benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9branched alkyl esters. Typically useful hydroperoxide decomposersinclude Sanko® HCA (9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide),triphenyl phosphate and other organo-phosphorous compounds, such as,Irgafos® TNPP from Ciba Specialty Chemicals, Irgafos® 168, from CibaSpecialty Chemicals, Ultranox® 626 from GE Specialty Chemicals, MarkPEP-6 from Asahi Denka, Mark HP-10 from Asahi Denka, Irgafos® P-EPQ fromCiba Specialty Chemicals, Ethanox 398 from Albemarle, Weston 618 from GESpecialty Chemicals, Irgafos® 12 from Ciba Specialty Chemicals, Irgafose38 from Ciba Specialty Chemicals, Ultranox® 641 from GE SpecialtyChemicals and Doverphos® S-9228 from Dover Chemicals.

When used as a clear coating or mono-coat composition, the novelcomposition optionally contains about 0.1-5% by weight, based on theweight of the binder, of hindered amine light stabilizers. Typicallyuseful hindered amine light stabilizers includeN-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-dodecyl succinimide, N(1acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecyl succinimide,N-(2hydroxyethyl)-2,6,6,6-tetramethylpiperidine-4-ol-succinic acidcopolymer, 1,3,5 triazine-2,4,6-triamine,N,N′″-[1,2-ethanediybis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl]]bis[N,N′″-dibutyl-N′,N′″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)],poly-[[6-[1,1,3,3-tetramethylbutyl)-amino]-1,3,5-trianzine-2,4diyl][2,2,6,6-tetramethylpiperidinyl)-imino]-1,6-hexane-diyl[(2,2,6,6-tetramethyl-4-piperidinyl)-imino]),bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[3,5bis(1,1-dimethylethyl-4-hydroxy-phenyl)methyl]butylpropanedioate,8-acetyl-3-dodecyl-7,7,9,9,-tetramethyl-1,3,8-triazaspiro(4,5)decane-2,4-dion,dodecyl/tetradecyl-3-(2,2,4,4-tetramethyl-21-oxo-7-oxa-3,20-diazaldispiro(5.1.11.2)henicosan-20-yl)propionate.

To form a coating composition that has a high level of weatherabilityand resistance to UV degradation, a combination of above describedultraviolet light absorbers, antioxidants and hindered amine lightstabilizers can be used.

Typically, the composition is a solvent based composition and any of theknown organic solvents may be used to form the coating composition.Typical solvents include aromatic hydrocarbons, such as, toluene,xylene; ketones, such as, acetone, methyl ethyl ketone, methyl isobutylketone, methyl amyl ketone and diisobutyl ketone; esters, such as, ethylacetate, n-butyl acetate, isobutyl acetate; and mixtures of any of theabove.

The novel coating composition may also include other conventionalformulation additives, such as, wetting agents, leveling and flowcontrol agents, for example, Resiflow®S (polybutylacrylate), BYK® 320and 325 (high molecular weight polyacrylates), BYK® 347(polyether-modified siloxane), rheology control agents, such as, fumedsilica, defoamers, surfactants and emulsifiers to help stabilize thecomposition. Other additives that tend to improve mar resistance can beadded, such as, silsesquioxanes and other silicate-basedmicro-particles.

The coating composition of this invention can be used as a clear coatthat is applied over a pigmented base coat that may a pigmented versionof the composition of this invention or another type of a pigmented basecoat. The clear coating can be in solution or in dispersion form.

Typically, a clear coating is then applied over the base coating beforethe base coating is fully cured, a so called “wet-on-wet process”, andthe base coating and clear coating are then fully cured at ambienttemperatures or can be cured by heating to elevated temperatures of 40°C. to 170° C. for 15 to 45 minutes. If used in refinishing vehicles, thebase coat may be allowed to “dry to the touch” at ambient temperatureconditions or under warm air before the clear coating is applied. Thebase coating and clear coating preferably have a dry coating thicknessranging from 25 to 75 microns and 25 to 100 microns, respectively. Also,the composition can be used as a matte clear coating composition that istypically applied to the interior of automobiles and trucks.

The novel coating composition may be used as a base coat or as apigmented monocoat topcoat. Both of these compositions require thepresence of pigments. Typically, a pigment-to-binder ratio of 0.1/100 to200/100 is used depending on the color and type of pigment used. Thepigments are formulated into mill bases by conventional procedures, suchas, grinding, sand milling, and high speed mixing. Generally, the millbase comprises pigment and a binder or a dispersant or both in asolventborne or aqueous medium. The mill base is added in an appropriateamount to the coating composition with mixing to form a pigmentedcoating composition.

Any of the conventionally-used organic and inorganic pigments, such as,white pigments, like, titanium dioxide, color pigments, metallic flakes,such as, aluminum flake, special effects pigments, such as, coated micaflakes, coated aluminum flakes and the like and extender pigments can beused. It may be desirable to add flow control additives.

The novel coating composition may be used as a primer or a sealer inwhich case typical pigments used in primers would be added, such as,carbon black, barytes, silica, iron oxide and other pigments that arecommonly used in primers in a pigment-to-binder ratio of 10/100 to300/100. These primers and sealers exhibit exceptional adhesion tountreated bare metal substrates, such as, aluminum and steel substrates,and to treated metal substrates, such as galvanized steel, and provideexcellent stone chip resistance.

The coating composition can be applied by conventional techniques, suchas, spraying, electrostatic spraying, dipping, brushing, and flowcoating.

The coating composition is particularly useful for the repair andrefinish of automobile bodies and truck bodies and parts as a clearcoat, pigmented base coat, mono-coat as a primer, sealer or primersurfacer.

The novel composition has also uses as binder for rapid cure chip coats.The novel composition of this invention can be combined with theisocyanate reagents described above directly without the use of asolvent or additional components and applied to an automobile bodydirectly using application methods known in the art such as integratedmulti-component applicators, spray guns or similar devices. Optionally,the combination of the composition of this invention including thetypical isocyanate component under simple agitation forms a mass with adesired viscosity profile for direct application to a surface, e.g., aputty, using spatulas or other manual application devices, such as asqueegee.

The novel composition has uses for coating any and all itemsmanufactured and painted by automobile sub-suppliers, frame rails,commercial trucks and truck bodies, including but not limited tobeverage bottles, utility bodies, ready mix concrete delivery vehiclebodies, waste hauling vehicle bodies, and fire and emergency vehiclebodies, as well as any potential attachments or components to such truckbodies, buses, farm and construction equipment, truck caps and covers,commercial trailers, consumer trailers, recreational vehicles, includingbut not limited to, motor homes, campers, conversion vans, vans, largecommercial aircraft and small pleasure aircraft, pleasure vehicles, suchas, snow mobiles, all terrain vehicles, personal watercraft,motorcycles, and boats. The novel composition also can be used as acoating for industrial and commercial new construction and maintenancethereof; cement and wood floors; walls of commercial and residentialstructures, such as, office buildings and homes; amusement parkequipment; concrete surfaces, such as parking lots and drive ways;asphalt and concrete road surface, wood substrates, marine surfaces;outdoor structures, such as bridges, towers; coil coating; railroadcars; printed circuit boards; machinery; OEM tools; signs; fiberglassstructures; sporting goods; and sporting equipment.

The following are testing procedures used in the Examples:

Cotton Tack Free Time

Allow coated panel to dry for set period of time (e.g. 30 minutes). Dropa cotton ball from a height of 1 inch onto the surface of the panel andleave the cotton ball on the surface for a set time interval and invertpanel. Repeat above until the time the cotton ball drops off the panelon inversion and note that as the cotton tack free time.

MEK Rubs

A coated panel is rubbed (100 times) with an MEK (methyl ethyl ketone)soaked cloth using a rubbing machine and any excess MEK is wiped off.The panel is rated from 1-10. Rating 10—no visible damage to thecoating, rating 9—1-3 distinct scratches, rating 8—4-6 distinctscratches, rating 7—7-10 distinct scratches, rating 6—10-15 distinctscratches with slight pitting or slight loss of color, rating 5—15-20distinct scratches with slight to moderate pitting or moderate loss ofcolor, rating 4—scratches start to blend into one another, rating 3—onlya few undamaged areas between blended scratches, rating 2—no visiblesigns of undamaged paint, rating 1 complete failure—bare spots areshown. The final rating is obtained by multiplying the number of rubs bythe rating.

Water Spot Test

Water spot rating is a measure of how well the film is crosslinked earlyin the curing of the film. If water spot damage is formed on the film,this is an indication that the cure is not complete and further curingof the film is needed before the film can be wet sanded or buffed ormoved from the spray both. The water spot rating is determined in thefollowing manner.

Coated panels are laid on a flat surface and deionized water was appliedwith a pipette at 1 hour-timed intervals. A drop about ½ inch indiameter was placed on the panel and allowed to evaporate. The spot onthe panel was checked for deformation and discoloration. The panel waswiped lightly with cheesecloth wetted with deionized water, which wasfollowed by lightly wiping the panel dry with the cloth. The panel wasthen rated on a scale of 1 to 10. Rating of 10 best—no evidence ofspotting or distortion of discoloration, rating 9—barely detectable,rating 8—slight ring, rating 7—very slight discoloration or slightdistortion, rating 6—slight loss of gloss or slight discoloration,rating 5—definite loss of gloss or discoloration, rating of 4—slightetching or definite distortion, rating of 3—light lifting, bad etchingor discoloration, rating of 2—definite lifting and rating of1—dissolving of the film.

BK Dry Time

Surface drying times of coated panels measured according to ASTMD5895-03.

Swell Ratio

The swell ratio of a free film (removed from a sheet ofTPO—thermoplastic olefin) was determined by swelling the film inmethylene chloride. The free film was placed between two layers ofaluminum foil and using a LADD punch, a disc of about 3.5 mm in diameterwas punched out of the film and the foil was removed from the film. Thediameter of the unswollen film (D_(o)) was measured using a microscopewith a 10× magnification and a filar lens. Four drops of methylenechloride were added to the film and the film was allowed to swell for afew second and then a glass slide was placed over the film and theswollen film diameter (D_(s)) was measured. The swell ratio was thencalculated as follow:Swell Ratio=(D _(s))²/(D _(o))²Persoz Hardness Test

The change in film hardness of the coating was measured with respect totime by using a Persoz hardness tester Model No. 5854 (ASTM D4366),supplied by Byk-Mallinckrodt, Wallingford, Conn. The number ofoscillations (referred to as Persoz number) were recorded.

Hardness (Fischer)

Hardness was measured using a Fischerscope® hardness tester (themeasurement is in Newtons per square millimeter).

Gel Fraction

Measured according to the procedure set forth in U.S. Pat. No. 6,221,494col. 8 line 56 to col. 9 line 2, which procedure is hereby incorporatedby reference.

Time to Gel

The time in minutes it takes for a liquid coating to gel.

Direct to Metal Adhesion Test

Adhesion of a coating to bare metal substrates was determined accordingto ASTM D3359-02, the standard test method for measuring adhesion bytape test.

The present invention is further defined in the following Examples. Itshould be understood that these Examples are given by way ofillustration only. From the above discussion and these Examples, oneskilled in the art can ascertain the essential characteristics of thisinvention, and without departing from the spirit and scope thereof, canmake various changes and modifications of the invention to adapt it tovarious uses and conditions. As a result, the present invention is notlimited by the illustrative examples set forth herein below, but ratheris defined by the claims contained herein below.

LC/MS (Liquid Chromatography/Mass Spectroscopy) analyses were performedon a Waters Alliance 2790 LC quipped with a MS (ES) interface. Column:Zorbax SB-C18, 2.1×150 mm at 50° C.; Solvents: A=99:1water/acetonitrile, B=acetonitrile, C=methanol, D=80:20acetonitrile/water; Conditions: 90% A/10% B/0.25% D to 0% A/100% B/0.25%D over 30 min, hold ten minutes, then return to initial conditions after42 min; Wavelength: 191-799 nm; Flow rate: 0.25 mL/min.

GC/MS (Gas Chromatography/Mass Spectroscopy) M was performed on anAgilent 6890 gas chromatograph coupled with Agilent 5973 MSD. A J & WScientific DB-5 capillary column was used. Helium was used as carriergas. The GC chromatography was programmed to start at 70 C for 4 mins,followed by temperature ramping to 300 C at rate of 10 C/min, the finaltemperature was hold for 7 mins. The entire run time was 34 mins. 1.0 ulsample solution was injected to obtain the desired chromatography,ionization method is EI.

EXAMPLE 1 Hydroformylation of2-methylbicyclo[2.2.1]hept-5-ene-2-carbonitrile

The hydroformylation catalyst was prepared by combining 0.31 gdicarbonylacetylacetonato rhodium(I) (1.2 mmol) and phosphite ligand(5.8 mmol) in 5 mL of toluene, forming under vigorous gas evolution aclear, yellow solution of phosphite acetylacetonato rhodium(I). Thecatalyst solution was added to 539 g of2-methyl-bicyclo-[2.2.1]hept-5-ene-2-carbonitrile (4.05 mol) in 200 mLof toluene, and the whole reaction mixture was charged into a 1 Lautoclave. The autoclave was heated to 85° C. and pressurized with 85psig CO/H₂ mixture for about 16 h, while the progress of the reactionwas periodically monitored by GC analysis. After venting the reactor,cooling to room temperature, and rinsing with methanol, solvent wasremoved from the reaction mixture by rotary evaporation, and theresidual yellow oil was distilled in vacuo to yield 567.5 g of5(6)-formyl-2-methylbicyclo[2.2.1]heptane-2-carbonitrile as colorlessliquid (86% isolated yield). Boiling point: 99.6° C. at 0.5 Torr. GC/MSanalysis revealed that the product was a mixture of severaldiastereomers.

EXAMPLE 2 A. Hydrogenation of (5 or6)-formyl-2-methylbicyclo[2.2.1]heptane-2-carbonitrile (Mixture ofIsomers) to (5 or6)-(hydroxymethyl)-2-methylbicyclo[2.2.1]heptane-2-carbonitrile

416 g of (5 or 6)-formyl-2-methylbicyclo[2.2.1]heptane-2-carbonitrile(2.55 mol) was dissolved in 200 g THF (tetrahydrofuran), 20 g catalyst,5% Ru on carbon (Aldrich), was added, and the whole reaction mixture wascharged into a 1 L autoclave. The autoclave was heated to 90° C. andpressurized with 1000 psig H₂ gas for 12 h while the progress of thereaction was periodically monitored by GC analysis. After venting thereactor, cooling to room temperature, and rinsing with THF, the reactionmixture was filtered though a plug of celite under nitrogen. Solvent wasremoved from the reaction mixture by rotary evaporation, and theresidual oil (388 g) was distilled in vacuo to yield 275 g (1.66 mol) of(5 or 6)-(hydroxymethyl)-2-methylbicyclo[2.2.1]heptane-2-carbonitrile ascolorless liquid (65% isolated yield). Boiling point: 93.3° C. at 80mTorr. The product was pure by GC/MS analysis.

B: Hydrogenation of (5 or6)-(hydroxymethyl)-2-methyl-bicyclo[2.2.1]heptane-2-carbonitrile to ((5or 6)-(aminomethyl)-5-methylbicyclo[2.2.1]heptan-2(3)-yl)methanol(Compound X)

435 g of (5 or6)-(hydroxymethyl)-2-methylbicyclo-[2.2.1]-heptane-2-carbonitrile (2.63mol) was dissolved in 150 mL methanol and 30 g catalyst slurry, Raney®2700 cobalt slurry in water (Aldrich), was added. The reaction mixturewas charged into a 1 L autoclave and 110 g ammonia (6.46 mol) was added.The autoclave was heated to 85° C. and pressurized with 1000 psig H₂mixture for at least 12 h while the progress of the reaction wasperiodically monitored by GC/MS analysis. After venting the reactor,cooling to room temperature, and rinsing with methanol, the reactionmixture was filtered though a plug of silica under nitrogen, and thesilica plug was rinsed with additional methanol. Solvent was removedfrom the reaction mixture by rotary evaporation, and the residual oil(389 g) was distilled in vacuo to yield 346 g (2.04 mol) of(5-(aminomethyl)-5-methylbicyclo[2.2.1]heptan-2(3)-yl)methanol (CompoundX) as colorless, viscous liquid (78% isolated yield). Boiling point: 98°C. at 12 mTorr. The product was pure by GC/MS analysis.

EXAMPLE 3 A. Hydrogenation of 2-methyl-2-cyano-(5 or6)-formyl-bicyclo[2.2.1]heptane to 2-methyl-2-cyano-(5 or6)-hydroxymethyl-bicyclo[2.2.1]heptane

To a 1 L pressure reactor were added 172 g starting nitrile-aldehyde,8.2 g of ESCAT 440 5% Ru/C, and 345 g THF. The reactor was sealed,purged with hydrogen and tested for leaks. The reactor was heated to 90°C. at which point the pressure was increased to 4826 kPa (700 psig) withhydrogen and the reaction commenced. Hydrogen was constantly replenishedfrom a cylinder and controlled by a forward pressure regulator. After6.25 hours the reaction was cooled. A gas chromatogram of the productshowed essentially full conversion to the nitrile alcohol and less than5% high boiling products. An infrared spectrum of the product revealedno carbonyl stretching bands but the presence of O—H stretching at 3421cm⁻¹. Nuclear magnetic resonance spectroscopy of the sample revealed thepresence of nitrile (127 ppm) and hydroxyl-substituted methylene (66ppm).

B. Hydrogenation of 2-methyl-2-cyano-(5 or6)-hydroxymethyl-bicyclo[2.2.1]heptane to 2-methyl-2-methyleneamine-(5or 6)-hydroxymethyl-bicyclo[2.2.1]heptane compound (X)

This is another procedure to form compound (X). To a 1 L pressurereactor were added 150 g of the product of example 2, 10 g of Raney® Co2724, approximately 10 g water, and 150 g methanol (to aid in transfer).The reactor was sealed, purged with hydrogen and tested for leaks andcooled. Ammonia (250 g) was added by distillation from a cylinder. Thereactor was heated to 85° C. at which point the pressure was increasedto 6895 kPa (1000 psig) with hydrogen and the reaction commenced.Hydrogen was constantly replenished from a cylinder and controlled by aforward pressure regulator. While not essential, the reactor wasmaintained at temperature and pressure for 10 hours at which time it wascooled. A gas chromatogram of the sample showed nearly quantitativeconversion to the desired amine-alcohol. An infrared spectrum of theproduct revealed no nitrile stretching absorbance (2235 cm⁻¹) but thepresence of amine N—H stretching absorbances around 3377 and

3297 cm⁻¹. NMR spectra revealed the absence of any nitrile peaks in the13C spectrum (˜125 ppm) and the formation of compound (XII). The productwas purified via distillation.

EXAMPLE 4 A: Hydrogenation of 3-ethyl-2-cyano-(5 or6)-formyl-bicyclo[2.2.1]heptane to 3-ethyl-2-cyano-(5 or6)-hydroxymethyl-bicyclo[2.2.1]heptane

To a 100 cc pressure reactor were added 32.1 g startingnitrile-aldehyde, 1.7 g of ESCAT 440 5% Ru/C, and 20 g THF. The reactorwas sealed, purged with hydrogen and tested for leaks. The reactor washeated to 100° C. at which point the pressure was increased to 3447 kPa(500 psig) with hydrogen and the reaction commenced. Hydrogen wasconstantly replenished from a 1-L reservoir and controlled by a forwardpressure regulator. After nearly 6 hours the reaction was cooled. Aninfrared spectrum of the product revealed no carbonyl stretching bandsbut the presence of O—H stretching at 3424 cm⁻¹. Nuclear magneticresonance spectroscopy of the sample revealed the presence of nitrile(124 ppm) and hydroxyl-substituted methylene (66-68 ppm).

B: Hydrogenation of 3-ethyl-2-cyano-(5 or6)-hydroxymethyl-bicyclo[2.2.1]heptane to 3-ethyl-2-methyleneamine-(5 or6)-hydroxymethyl-bicyclo[2.2.1]heptane compound (XIII)

To a 1 L pressure reactor were added 150 g of the product of example 3A,10 g of Raney® Co 2724, approximately 10 g water, and 150 g methanol (toaid in transfer). The reactor was sealed, purged with hydrogen andtested for leaks and cooled. Ammonia (250 g) was added by distillationfrom a cylinder. The reactor was heated to 85° C. at which point thepressure was increased to 6895 kPa (1000 psig) with hydrogen and thereaction commenced. Hydrogen was constantly replenished from a cylinderand controlled by a forward pressure regulator. While not essential, thereactor was maintained at temperature and pressure for 10 hours at whichtime it was cooled. A gas chromatogram of the sample showed nearlyquantitative conversion to the desired amine-alcohol. An infraredspectrum of the product revealed no nitrile stretching absorbance (2235cm⁻¹) but the presence of amine N—H stretching absorbances around 3377and 3297 cm⁻¹. NMR spectra revealed the absence of any nitrile peaks inthe ¹³C spectrum (˜125 ppm) and the formation of compound (XIII). Theproduct was purified via distillation.

EXAMPLE 5

Synthesis of Compound Represented by Formula (XXII).

To a four-necked 1000 mL round bottom flask fitted with magneticstirrer, thermocouple, condenser and addition funnel was added undernitrogen atmosphere 50.9 g of 6-amino-1-hexanol (97%, 0.43 mol) followedby 450 mL of dry methylene chloride. Then 99.1 g (0.43 mol) di-secbutylmaleate was slowly added via the addition funnel while maintaining thetemperature below 20° C. The pale yellow reaction mixture was stirred atroom temperature over night, and the progress of the reaction wasmonitored by GC (disappearance of 6-amino-1-hexanol) and LC analysis.The reaction mixture was concentrated to about 200 mL, filtered on amedium frit to remove haze (di-secbutyl fumarate), then solvent wasremoved in vacuo to constant weight, yielding 149.1 g of a yellow, clearoil. LC/MS analysis: 12.94 min (M+H=346, 93.3%); 14.08 min (M+H=617,2.3%, double addition product); 21.06 min (M+H=501, 2.0%,transesterification product).

EXAMPLE 6

Synthesis of Compound Represented by Formula (XXV).

To a glass vial with magnetic stirrer was added under nitrogenatmosphere 6.2 g of (4-(aminomethyl)cyclohexyl)methanol (0.04 mol). Thevial was cooled to 0° C. and 9.9 g (0.04 mol) di-secbutyl maleate wasslowly added via pipette. The reaction mixture was placed in a heatingblock and stirred at 50° C. room temperature over night, and theprogress of the reaction was monitored by GC (disappearance of startingmaterials) and LC analysis. The aspartic aminoalcohol XXV was obtainedas clear oil in quantitative yield. LC/MS analysis: 14.11, 14.44 min(M+H=372,18.1%, 48.3%); 20.16 min (M+H=614, 29.7%, unknown).

EXAMPLE 7

Synthesis of Compound Represent by Formula (XXIX).

To a four-necked 1 L round bottom flask fitted with magnetic stirrer,thermocouple, condenser and addition funnel was added under nitrogenatmosphere 148.7 g of(5-(aminomethyl)-5-methyl-bicyclo-[2.2.1]-heptan-2(3)-yl)methanol (0.879mol) and 200 mL of dry acetonitrile. The solution was cooled to 0° C.and 151.3 g diethylmaleate (0.879 mol) (maleic acid diethylester,Aldrich) was added dropwise over 40 minutes while maintaining thetemperature below 3° C. The reaction mixture was then allowed to warm upto room temperature and stirred for three days, while the progress ofthe reaction was monitored by GC (disappearance of starting materials)and LC/MS analysis. Solvent was removed by rotary evaporation, and theresidual colorless oil (299.2 g) was dried in vacuo. 190.3 g of (XXIX)was isolated as colorless oil after solvent removal and filtrationthrough celite. GC analysis: 22.04, 22.12, 22.41 min (23.6%, 14.9%,58.4%, all AAO 2). LC/MS analysis (ES) confirms exclusively desiredproduct (M+H=342.3), no primary or tertiary amine detected.

EXAMPLE 8

Synthesis of Compound Represented by Formula (XXX).

To a four-necked 250 mL round bottom flask fitted with magnetic stirrer,thermocouple, condenser and addition funnel was added under nitrogenatmosphere 70.8 g of (X) (0.418 mol). Then 99.4 g (0.418 mol) dibutylmaleate (Aldrich) was slowly added via the addition funnel while thetemperature gradually increased to about 50° C. The reaction mixture wasthen heated to 70° C. for about 24 h, while the progress of the reactionwas monitored by GC and LC analysis. After cooling to room temperature,166.0 g of the desired product (XXX) was obtained as clear and colorlessoil.

LC/MS analysis confirms desired product (M+H=398.3) in >97% purity.

EXAMPLE 9

Synthesis of Compound Represented by Formula (XXXI).

To a four-necked 500 mL round bottom flask fitted with magnetic stirrer,thermocouple, condenser and addition funnel was added under nitrogenatmosphere 100.0 g of(5-(aminomethyl)-5-methyl-bicyclo-[2.2.1]-heptan-2(3)-yl)methanol (0.59mol). Then 134.9 g (0.59 mol) di-secbutyl maleate was slowly added viathe addition funnel while the temperature gradually increased to about44° C. The reaction mixture was then heated to 70° C. for 60 hours,while the progress of the reaction was monitored by GC (disappearance ofstarting materials) and LC analysis. After cooling to room temperature,229.5 g of di-sec-butyl2-((5-(hydroxymethyl)-2-methylbicyclo[2.2.1]heptan-2-yl)-methylamino)-succinatewas obtained as pale yellow, clear oil. LC/MS analysis: 13.76 min, 14.58min (M+H=398.3).

EXAMPLE 10

Synthesis of Compound Represented by Formula (XXXII).

To a four-necked 2 L round bottom flask fitted with magnetic stirrer,thermocouple, condenser and addition funnel was added under nitrogenatmosphere 187.1 g of dicyclohexyl-maleate (0.667 mol) (maleic aciddicyclohexylester) and 800 mL of dry acetonitrile. 112.9 g of(5-(aminomethyl)-5-methyl-bicyclo-[2.2.1]-heptan-2(3)-yl)methanol (0.667mol) was slowly added via the addition funnel, which was gently heatedto facilitate the addition of the viscous liquid, and finally rinsedwith a few mL of acetonitrile. The solution was heated to 50° C. andstirred for 60 hours, while the progress of the reaction was monitoredby GC (disappearance of starting materials) and LC/MS analysis. Solventwas removed by rotary evaporation yielding a yellow oil (299.9 g). Thecrude material was purified by flash chromatography on silica gel (10%ethyl acetate in hexane). 208.2 g of (XXXII) was isolated as highlyviscous and hazy liquid after solvent removal and filtration throughcelite. GC analysis: 19.46 min (0.4%, Cy maleate); 20.09 min (3.2%, Cyfumarate); 28.68, 29.06, 29.52 min (5.5%, 34.0%, 55.8%). LC/MS analysis(ES) confirms exclusively desired product (M+H=450.2), no primary ortertiary amine detected.

EXAMPLE 11

Synthesis of Compound Represented by Formula (XXXIII).

To a four-necked 1 L round bottom flask fitted with magnetic stirrer,thermocouple, condenser and addition funnel was added under nitrogenatmosphere 64.0 g of dicyclohexyl-maleate (0.228 mol) (maleic aciddicyclohexylester), 400 mL of dry acetonitrile and 46.0 g compound (XVI)(0.254 mol). The solution was heated to 60° C. and stirred for about 24h, while the progress of the reaction was monitored by GC and LC/MSanalysis. The reaction mixture was filtered through a medium frit beforesolvent was removed by rotary evaporation yielding (XXXIII) as acolorless oil (111.2 g). GC analysis: 15.10, 15.29, 15.49 min; 19.49 min(1.0%, Cy maleate); 20.14 min (15.1%, Cyfumarate); 32.00, 32.53, 33.80min LC/MS (ES) confirms desired product (M+H=462.3, ca. 93% by MS).

The Brookfield viscosity of a solution of commercial available diamine,Desmophen® NH-1420 (Bayer), to the viscosity of NCO reactive componentsXXIX (Example 6) and XXX (Example 7) were compared.

The results are as follows:

NCO reactive component/composition Brookfield Viscosity Des. NH1420Composition 1000 cps XXIX (Ex. 6) Composition  514 cps XXX (Ex. 7)Composition  665 cpsDesmophen® NH-1420—reaction product of 4,4′-methylene-biscyclohexanamineand diethyl maleate (Bayer-1000 cps).

These viscosity measurements show a much lower viscosity of the NCOReactive Component (XXIX) and (XXX) of this invention in comparison tothe viscosity of Desmophen® NH-1420 (Bayer). The high viscosity ofDesmophen® NH-1420 requires the use of low viscosity, reactive diluents,such as, ketimines for the formulation of true 2.1 VOC systems. Becauseof the surprisingly low viscosity of a number of the NCO reactivecomponents (aspartic amino-alcohols) of this invention, they can beformulated without the addition of reactive diluents.

EXAMPLE 12

Coating Compositions 12A-12E Were Prepared as Follows: CoatingComposition 12A 12B 12C 12D 12E Portion 1 NCO Reactive 20 — — — —Component (XXIX) Example 7 NCO Reactive — 20 — — — Component (XXX)Example 8 NCO Reactive — — 19.72 — — Component (XXXI) Example 9 NCOReactive — — — 15 — Component (XXII) Example 5 NCO Reactive — — — — 20Component (XXXII) Example 10 Butyl Acetate 14.86 13.64 14.20 9.84 13.56Flow Additive¹ 0.48 0.44 0.39 0.32 0.38 Catalyst Solution² 4.48 4.431.96 3.20 1.88 Acetic Acid 0.58 0.53 0.24 0.38 0.23 Portion 2 Tolonate ®HDT³ 28.43 24.43 19.46 17.05 17.45 ¹Flow additive-20% BYK 301 ® flowadditive, supplied by BYK CHEMIE, in propylene glycol monomethyl etheracetate. ²Catalyst Solution-1% DBTDL (dibutyl tin dilaurate) in methylethyl ketone. ³Tolonate HDT-isocyanurate trimer of hexamethylenediisocyanate supplied by Rhodia Inc.

For each of Examples 12A-12E, the constituents of Portion 1 were chargedinto a mixing vessel and then Portion 2 was charged into the mixingvessel and thoroughly mixed with Portion 1. Each of the coatingcompositions 12A-12E was applied with a doctor blade over a separatephosphated cold roll steel panel primed with a layer of PowerCron®Primer supplied by PPG, Pittsburgh, Pa., to a dry coating thickness ofabout 50 micrometers and air dried at ambient temperature conditions.Then the panels were tested using the test set forth in following Table2 and the results of the test are shown in this table.

TABLE 2 Coating Composition 12A 12B 12C 12D 12E NCO Reactive Comp. XXIXXXX XXXI XXII XXXII Theo. Eq. Wt. 171 199 199 172.7 225 Calculated Wt.Solids 70% 70% 70% 70% 70% Time to gel (min.) 114 150 101 150 83 BK 3time (min.) 86.2 75.6 111 73.23 151 BK 4 time (min.) 354 99 475 108.66210 Cotton tack free time 114 69 180 105 >300 (min.) Water spot-4hrs. @8 8 9 9 8 Room. Temp. MEK rubs-4hrs @ 600 800 600 100 750 Room Temp.Swell Ratio-1 day @ 1.93 1.99 1.93 1.87 1.90 Room Temp. Swell Ratio-30day @ 1.90 1.99 1.87 1.96 1.82 Room Temp. Persoz hardness-4 hrs @ 20 3019 27 18 Room Temp. Fischer Hardness-1 day 9.40 14.85 11.00 13.80 4.70 @Room Temp. Fischer Hardness-30 days 30.8 70.0 44.0 23.3 13.4 @ RoomTemp. Gel Fraction-30 days 94.78 95.00 93.54 95.23 87.83 Room Temp.Theo. Eq. Wt. - theoretical equivalent weight. Min. - minutes

The results for coating compositions 12A-12E show that coatings madefrom the NCO Reactive Components of this invention have excellent earlycure, as is evident from the short BK dry times, excellent early waterspot, and good MEK rubs at 4 hours and remain fluid for a useful periodof time. NCO Reactive Compound (XXX) is particularly useful with a timeto gel of 150 minutes and good early cure. The films also have excellentfinal properties such as hardness and gel fraction.

EXAMPLE 13

Coating Compositions 13A-13D Were Prepared as Follows: CoatingComposition 13A 13B 13C 13D Portion 1 NCO Reactive 20 20 20 20 Component(XXX) Example 8 Butyl acetate 15.6 12.14 12.63 15.79 Flow Additive 0.440.44 0.44 0.44 (described in Ex. 12) Portion 2 Tolonate ® HDT 19.7319.73 19.73 19.73 (described in Ex. 12) Portion 3 Catalyst Solution 0.993.97 0 0 (described in Ex. 12) Acetic acid 0 0.48 0 0 10% DABCO⁴ inxylene 0 0 3.96 0 25% DMEA⁵ in methyl 0 0 0 0.8 ethyl ketone⁴DABCO-1,4-diazabicyclo(2.2.2)octane ⁵DMEA-dimethyl ethanol amine

For each of Examples 13A-13D, the constituents of Portion 1 were chargedinto a mixing vessel in the order shown above and mixed then Portion 2was charged into the mixing vessel and thoroughly mixed with Portion 1.Portion 3 was then added with mixing. Each of the coating compositionswas applied with a doctor blade over a separate phosphated cold rollsteel panel primed with a layer of PowerCron® Primer supplied by PPG,Pittsburgh, Pa., to a dry coating thickness of about 50 micrometers andair dried at ambient temperature conditions. A second set of panels werecured for 20 minutes at 60° C. Then the panels were tested using thetest set forth in following table and the results of the test are shownin Table 3 below.

TABLE 3 Coating Composition 13A 13B 13C 13D NCO Reactive Comp. XXX XXXXXX XXX Theo. Eq. Wt. 199 199 199 199 Calculated Wt. Solids 70% 70% 70%70% Catalyst (on binder) 250 1000 1% 0.5% ppm ppmDBTD DABCO DMEA DBTDL L& 1.2% cetic acid Time to gel (min.) 51 84 146 193 BK 3 time (min.) 31998 63.8 260 BK 4 time (min.) >692 239 201 >633 Water spot-4 hrs. @ 7 9 95 Room. Temp. MEK rubs-4 hrs @ Room 300 600 700 400 Temp. PersozHardness-4 hrs 19 8 33 tacky @ Room Temp. Persoz Hardness-20 min. 243 35101 130 @ 60° C. bake on cool down Fischer Hardness-1 day 38.6 8.2 9.431 @ Room Temp. Fischer Hardness-30 days 75.3 25.2 11.3 55.0 @ RoomTemp. Fischer Hardness-after 94 Too soft 2.1 29 20 min @ 60° C. on cooldown Fischer Hardness-1 day 145 8.11 19 79 after 20 min @60 ° C. FischerHardness-30 days 86.1 31 17 104 after 20 min @ 60° C. Theo. Eq. Wt. -theoretical equivalent weight ppm - parts per million min. - minutes

Coating compositions 13A-13D show that compositions made from the NCOReactive Components of this invention may be catalyzed by a variety ofcatalysts, including tertiary amines. The systems made using DABCO andDMEA have excellent early cure, as is evident from the short BK drytimes, excellent early water spot, and good MEK rubs at 4 hours and havea significantly long time to gel (146 to 193 minutes). These types ofcatalysts are particularly useful when curing at slightly elevatedtemperatures for short times, such as, 20 minutes at 60° C. The filmsalso have good final properties, such as, hardness.

EXAMPLE 14

(Direct-to-Metal Adhesion):

In the following Example, the reactive isocyanate compound XXXI wascombined with Desmodur® 3300 and 250 ppm DBTDL at 70% weight in butylacetate in a 30 mm vial and vortexed for 20 seconds. The coatingcomposition was applied with a doctor blade (5 mil film) over A) clean,unpolished aluminum, B) clean, unpolished cold roll steel, and C) clean,unpolished galvanized steel. The adhesion of the coating film wasmeasured according to the aforementioned “X-hatch” tape test after 1day, 3 days and seven days. The results are summarized in the attachedtable, showing excellent adhesion (10=highest rating) for cold rollsteel and galvanized steel, and almost the same excellent adhesion toaluminum.

Compound XXXI Day 1 Tape Day 3 Day 7 Plates used Rating Plates RatingPlates Rating A 898 9 A 9 A 9 B 898 10 B 10 B 10 C 898 10 C 10 C 10

EXAMPLE 15

Synthesis of Compound Represented by Formula (XXXIV)

To a four-neck 5000 mL RBF fitted with overhead stirrer, additionfunnel, reflux condenser, and thermocouple, under N₂, was added2-(2-aminoethoxy)-ethanol (BASF) (632.0 g, 6.01 mol, 1 eq.), followed bythe dropwise addition of sec-butyl maleate (1370.0 g, 6.00 mol, 1 eq.),maintaining <15-20° C. The reaction was stirred overnight at roomtemperature. The next morning, a GC analysis showed no startingmaterial. LC/MS(ES+) confirmed the presence of the desired product,which was isolated in 97% yield.

EXAMPLE 16

Synthesis of Compound Represented by Formula (XXXVI)

To a four-neck 2000 mL RBF fitted with overhead stirrer, additionfunnel, reflux condenser, and thermocouple, under N₂, was addedbis-(2-hydroxypropyl)aminopropylamine (Tomah) (323.0 g, 1.70 mol, 1eq.), followed by the dropwise addition of sec-butyl maleate (387.5 g,1.70 mol, 1 eq.), maintaining <30° C. The reaction was heated to 50° C.and was stirred overnight at that temperature. GC and LC/MS (ES+) showedvery little starting material by morning. The dark yellow oil was cooledto room temperature, and analysis via LC/MS (ES+) showed the resultingproduct to be 94.7% pure.

EXAMPLE 17

Coating Composition 17 was Prepared as Follows: Coating CompositionPortion 1 NCO Reactive Component (XXXVI) Example 16 13.95 Butyl Acetate10.29 Flow Additive¹ 0.34 Catalyst Solution² 3.36 Acetic Acid 0.40Portion 2 Tolonate ® HDT³ 19.64 ¹Flow additive-20% BYK 301 ® flowadditive, supplied by BYK CHEMIE, in propylene glycol monomethyl etheracetate. ²Catalyst Solution-1% DBTDL (dibutyl tin dilaurate) in methylethyl ketone. ³Tolonate HDT-isocyanurate trimer of hexamethylenediisocyanate supplied by Rhodia Inc.

The constituents of Portion 1 were charged into a mixing vessel and thenPortion 2 was charged into the mixing vessel and thoroughly mixed withPortion 1. The coating composition was applied with a doctor blade overa separate phosphated cold roll steel panel primed with a layer ofPowerCron® Primer supplied by PPG, Pittsburgh, Pa., to a dry coatingthickness of about 50 micrometers and air dried at ambient temperatureconditions. Then the panels were tested using the test set forth infollowing Table 4 and the results of the test are shown in this table.

TABLE 4 Coating Composition 17 NCO Reactive Comp. XXXVI Theo. Eq. Wt.139.5 Calculated Wt. Solids 70% Time to gel (min.) 112 BK 3 time (min.)80.3 BK 4 time (min.) 106 Cotton tack free time (min.) 117 Waterspot-4hrs. @ Room. Temp. 10 MEK rubs-4hrs @ Room Temp. 600 Swell Ratio-1day @ Room Temp. 1.77 Swell Ratio-30 day @ Room Temp. 1.77 Persozhardness-4 hrs @ Room Temp. 19 Fischer Hardness-1 day @ Room Temp. 7.1Fischer Hardness-30 days @ Room Temp. 11.8 Gel Fraction-30 days @ RoomTemp. 93.82 Theo. Eq. Wt. - theoretical equivalent weight. Min. -minutes

The results for coating composition 17 shows that coatings made from theNCO Reactive Components of this invention have excellent early cure, asis evident from the short BK dry times, excellent early water spot, andgood MEK rubs at 4 hours and remain fluid for a useful period of time.NCO Reactive Compound (XXXVI) is particularly useful with atri-functional structure that exhibits an excellent BK4 dry time of 106minutes and a 1 day swell ratio of 1.77.

1. A coating composition comprising Component A comprising apolyisocyanate crosslinking agent; and Component B comprising anisocyanate-reactive component having at least one compound having thefollowing formula:

wherein X can be independently O or N; when X equals O, n equals 1 andwhen X equals N, n equals 2; wherein R¹ is independently selected fromH, a C₁ to C₂₀ linear or branched alkyl group, a C₅ to C₁₆cycloaliphatic group, a phenyl group, a C₆ to C₂₀ aryl group substitutedwith a C₁ to C₁₂ alkyl group, wherein m on average equals 1, 2 or 3,wherein R² comprises a compound having the following formula (V)

wherein k equals 0, 1 or 2 and, when k equals 1 or 2, the additionalbridging CH₂ group(s) may be on the same or opposite side with respectto the first bridging CH₂ group; B equals(—(CH₂)_(t)—(CH)—(CH₂)_(s)—)_(r), r=0 or 1, s+t=1 to 16, with the —(CH)—group connecting to the —(CH₂)_(g)— group, in which B forms a ring inplace of one of R²⁰, R²¹ or R²² substituents; R²⁰, R²¹, and R²² can bethe same or different and are each independently H, a C₁ to C₂₀ linearor branched alkyl group; q is equal to 1, 2, 3, or 4; R²³, R²⁴, R²⁵ andR²⁶ can be the same or different and are each independently H, a C₁ toC₂₀ linear or branched alkyl group; with the proviso that at least onesubstituent independently selected from R²³, R²⁴, R²⁵ and R²⁶ is a —OHgroup, or a C₁ to C₂₀ linear or branched alkyl group bearing a hydroxylgroup; and wherein p on average equals 1, 2 or
 3. 2. A coatingcomposition comprising Component A comprising a polyisocyanatecrosslinking agent; and Component B comprising an isocyanate-reactivecomponent wherein Component B comprises at least one compound selectedfrom the group consisting of;

or a combination thereof.
 3. The coating composition of claim 1 or 2wherein component B further comprises a polymeric component having anumber average molecular weight of 5,000 to 50,000 and having reactivegroups that crosslink with an isocyanate, where the reactive groups areselected from the group consisting of hydroxyl, carboxyl, glycidyl,amine and any mixtures thereof.
 4. The coating composition of claim 1 or2 wherein component B further comprises an oligomeric component having anumber average molecular weight of 300 to 3,000 having reactive groupsthat crosslink with an isocyanate, where the reactive groups arehydroxyl, carboxyl, glycidyl, amine, aldimines, phosphoric acid,ketimine and any mixtures thereof.
 5. The coating composition of claim 1or 2 wherein component B further comprises 1 to 60% by weight, based onthe weight of the binder, of an acrylic polymer having a number averagemolecular weight of 5,000 to 50,000 and having groups reactive withisocyanate.
 6. The coating composition of claim 5 where the acrylicpolymer consists essentially of polymerized monomers selected from thegroup consisting of linear alkyl (meth)acrylates having 1 to 12 carbonatoms in the alkyl group, cyclic or branched alkyl (meth)acrylateshaving 3 to 12 carbon atoms in the alkyl group, isobornyl(meth)acrylate, styrene, alpha methyl styrene, vinyl toluene,(meth)acrylonitrile, (meth)acryl amides and mixtures thereof, andpolymerized monomers that provide groups reactive with isocyanateselected from the group consisting of hydroxy alkyl (meth)acrylates,glycidyl (meth)acrylates, amino alkyl(meth)acrylates and (meth)acrylicacid.
 7. The coating composition of claim 5 wherein the acrylic polymerhas a hydroxyl equivalent weight of 300 to 1300 and consists essentiallyof polymerized monomers selected from the group consisting of alkyl(meth)acrylates having 1 to 12 carbon atoms in the alkyl group, cyclicor branched alkyl (meth)acrylates having 3 to 12 carbon atoms in thealkyl group, isobornyl methacrylate, styrene, alpha methyl styrene,(meth)acrylonitrile, (meth)acryl amides, and polymerized monomersconsisting of hydroxy alkyl (meth)acrylates having 1 to 4 carbon atomsin the alkyl group.
 8. The coating composition of claim 1 or 2 whereincomponent B further comprises 1 to 60% by weight, based on the weight ofthe binder, of an acrylic oligomer having a number average molecularweight of 300 to 3,000 and having groups reactive with isocyanateselected from the group consisting of hydroxyl, carboxyl, glycidyl,amine, aldimines, phosphoric acid, ketimine and any mixtures thereof. 9.The coating composition of claim 8 wherein the acrylic oligomer consistsessentially of polymerized monomers selected from the group consistingof linear alkyl (meth)acrylates having 1 to 12 carbon atoms in the alkylgroup, cyclic or branched alkyl (meth)acrylates having 3 to 12 carbonatoms in the alkyl group, isobornyl (meth)acrylate, styrene, alphamethyl styrene, vinyl toluene, (meth)acrylonitrile, (meth)acryl amides,and polymerized monomers that provide groups reactive with isocyanateselected from the group consisting of hydroxy alkyl (meth)acrylates,glycidyl (meth)acrylates, amino alkyl(meth)acrylates and (meth)acrylicacid and a combination thereof.
 10. The coating composition of claim 1or 2 wherein the binder contains 1 to 60% by weight, based on the weightof the binder, of a polyester having hydroxyl groups.
 11. The coatingcomposition of claim 1 or 2 wherein component B further comprises 1 to60% by weight, based on the weight of the binder, of a urethane oligomerthat is the reaction product of a polyisocyanate selected from the groupconsisting of an aliphatic polyisocyanate and a cycloaliphaticpolyisocyanate; a hydroxy functional aliphatic carboxylic acid and amonohydric alcohol selected from the group consisting of aliphaticmonohydric alcohol and cycloaliphatic monohydric alcohol.
 12. Thecoating composition of claim 11 wherein the urethane oligomer consistsessentially of the reaction product of the isocyanurate of hexanediisocyanate, cyclohexanol, dimethylol propionic acid.
 13. The coatingcomposition of claim 1 or 2 wherein component B further comprises about1 to 30% by weight, based on the weight of the binder, of an acrylicnon-aqueous dispersed resin.
 14. The coating composition of claim 1 or 2wherein the polyisocyanate crosslinking agent is selected from the groupconsisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanates,aromatic polyisocyanates and isocyanate adducts.
 15. The coatingcomposition of claim 1 or 2 wherein the polyisocyanate is selected fromthe group consisting of isophorone diisocyanate, hexamethylenediisocyanate, and trimers of hexamethylene diisocyanate or isophoronediisocyanate.
 16. The coating composition of claim 1 or 2 wherein thecoating composition further comprises at least one additive selectedfrom the group consisting of ultraviolet light absorbers, antioxidants,hindered amine light stabilizers, catalysts, and a combination thereof.17. The coating composition of claim 16 wherein the catalyst is selectedfrom the group consisting of a tin compound, a tertiary amine, an acidcatalyst and a combination thereof.